CN110475838B - Polymer for liquid crystal aligning agent, liquid crystal aligning agent composition comprising same, liquid crystal aligning film using same, and liquid crystal display device - Google Patents

Polymer for liquid crystal aligning agent, liquid crystal aligning agent composition comprising same, liquid crystal aligning film using same, and liquid crystal display device Download PDF

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CN110475838B
CN110475838B CN201880020048.5A CN201880020048A CN110475838B CN 110475838 B CN110475838 B CN 110475838B CN 201880020048 A CN201880020048 A CN 201880020048A CN 110475838 B CN110475838 B CN 110475838B
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liquid crystal
chemical formula
aligning agent
crystal aligning
crystal alignment
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CN110475838A (en
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金成九
韩�熙
曹正镐
闵盛晙
权纯湖
尹陖荣
尹亨硕
朴训绪
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LG Chem Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
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    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/027—Polyimide

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Abstract

The present invention relates to a polymer excellent in liquid crystal alignment characteristics, durability, and electrical characteristics and thus suitable for use in a liquid crystal alignment agent, a liquid crystal alignment agent composition comprising the same, a liquid crystal alignment film formed from the liquid crystal alignment agent composition, and a liquid crystal display device including the liquid crystal alignment film.

Description

Polymer for liquid crystal aligning agent, liquid crystal aligning agent composition comprising same, liquid crystal aligning film using same, and liquid crystal display device
Technical Field
Cross Reference to Related Applications
The present application claims priority and equity to korean patent application No. 10-2017-0107525 filed on the 24 th month of 2017 to korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a polymer excellent in liquid crystal alignment characteristics, durability, and electrical characteristics and thus suitable for use in a liquid crystal alignment agent, a liquid crystal alignment agent composition comprising the same, a liquid crystal alignment film formed from the liquid crystal alignment agent composition, and a liquid crystal display device including the liquid crystal alignment film.
Background
In order to obtain uniform brightness and high contrast in a liquid crystal display device, it is necessary to uniformly orient the liquid crystal. The liquid crystal alignment agent acts as a director in the alignment of liquid crystal molecules and makes it possible to orient the liquid crystal in an appropriate direction when it moves due to an electric field to form an image.
Polyimide, polyamide, polyester, and the like are well known as conventional liquid crystal aligning agents. Among them, polyimide has been used for many liquid crystal display devices, particularly, because it has excellent heat resistance, liquid crystal affinity, mechanical strength, and the like.
However, recently, as the demand for low power displays increases, it has been found that a liquid crystal aligning agent may affect not only basic characteristics of liquid crystal alignment but also electrical characteristics such as afterimage (after-image) or voltage holding ratio caused by DC/AC voltage. Accordingly, there is an increasing need to develop a liquid crystal alignment material capable of achieving both excellent liquid crystal alignment characteristics and electric characteristics.
For this purpose, various attempts have been made to improve physical/chemical characteristics of the liquid crystal aligning agent by changing the structure of the liquid crystal aligning agent, for example, by a method of modifying a monomer used for producing the liquid crystal aligning agent, a method of combining a plurality of different monomers, and the like, but significantly improved physical characteristics have not been achieved yet.
Therefore, development of a new liquid crystal aligning agent having excellent liquid crystal alignment characteristics, durability and electric characteristics is required.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a polymer which is excellent in liquid crystal alignment characteristics, durability and electric characteristics and thus suitable for use in a liquid crystal aligning agent.
Another object of the present invention is to provide a liquid crystal aligning agent composition, a liquid crystal aligning film and a liquid crystal display device using the above polymer for a liquid crystal aligning agent.
Technical proposal
In order to achieve the above object, the present invention provides a polymer for a liquid crystal aligning agent, comprising at least one selected from the group consisting of: a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3.
[ chemical formula 1]
Figure GDA0003922747360000021
[ chemical formula 2]
Figure GDA0003922747360000022
[ chemical formula 3]
Figure GDA0003922747360000031
In chemical formulas 1 to 3, R 1 And R is 2 In (a) and (b)At least one is an alkyl group having 1 to 10 carbon atoms and the remainder are hydrogen, X 1 To X 3 Each independently is a tetravalent organic group, and Y 1 To Y 3 Each independently is a divalent organic group represented by the following chemical formula 4,
[ chemical formula 4]
Figure GDA0003922747360000032
Wherein in chemical formula 4, Q 1 To Q 4 At least one of which is nitrogen and the rest is carbon, Q 5 To Q 8 At least one of which is nitrogen and the others are carbon, and R 3 Is hydrogen or an alkyl group having 1 to 6 carbon atoms.
Hereinafter, a polymer for a liquid crystal aligning agent and a method of preparing the same according to one embodiment of the present invention will be described in more detail.
Throughout this specification, when a portion "comprises" an element, unless specifically stated otherwise, this is not intended to exclude additional elements, but rather is intended to include additional elements as well.
As used herein, the term "substituted" means that the hydrogen atom bonded to a carbon atom in the compound is replaced with another substituent, and the position to be substituted is not limited as long as the position is the position where the hydrogen atom is substituted (i.e., the position where the substituent may be substituted), and when two or more substituents may be the same or different from each other.
As used herein, the term "substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium; a halogen group; cyano group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; an amino group; a carboxyl group; a sulfonic acid group; sulfonamide groups; a phosphine oxide group; an alkoxy group; an aryloxy group; alkylthio; arylthio; an alkylsulfonyl group; arylsulfonyl; a silyl group; a boron base; an alkyl group; cycloalkyl; alkenyl groups; an aryl group; an aralkyl group; aralkenyl; alkylaryl groups; aryl phosphino; or a heterocyclic group comprising at least one of N, O and S atoms, or a substituent that is unsubstituted or linked via two or more of the substituents exemplified above. For example, a "substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl may also be aryl, and may be interpreted as two substituents to which phenyl is attached.
In the present specification, symbols
Figure GDA0003922747360000041
Meaning a bond to another substituent, and a direct bond means a case where no separate atom is present at the moiety represented by L.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 10. According to another exemplary embodiment, the alkyl group has a carbon number of 1 to 6. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cycloheptylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.
The fluoroalkyl group having 1 to 10 carbon atoms may be a group in which at least one hydrogen in an alkyl group having 1 to 10 carbon atoms is substituted with fluorine, and the fluoroalkoxy group having 1 to 10 carbon atoms may be a group in which at least one hydrogen in an alkoxy group having 1 to 10 carbon atoms is substituted with fluorine.
Halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).
Nitrogen oxides are compounds in which nitrogen atoms and oxygen atoms are bonded, and nitrogen oxidesBy a functional group is meant a functional group comprising a nitroxide in the functional group. As examples of nitroxide functionalities, nitro (-NO) groups can be used 2 ) Etc.
Polymer for liquid crystal aligning agent
The present inventors have found through experiments that when a polymer for a liquid crystal aligning agent comprising repeating units of chemical formulas 1 to 3 prepared from a reactant comprising a diamine compound having a specific structure is used, excellent liquid crystal alignment characteristics and high voltage holding rate at high temperature can be provided, and afterimage phenomenon or deterioration of contrast can be improved, thereby completing the present invention.
Specifically, according to one embodiment of the present invention, there may be provided a polymer for a liquid crystal aligning agent, which comprises at least one repeating unit selected from the group consisting of: a repeating unit represented by chemical formula 1, a repeating unit represented by chemical formula 2, and a repeating unit represented by chemical formula 3.
That is, the polymer for the liquid crystal aligning agent may include one type of the repeating unit represented by chemical formula 1, one type of the repeating unit represented by chemical formula 2, one type of the repeating unit represented by chemical formula 3, or a mixture of two or more thereof.
In particular, Y 1 To Y 3 Each is defined as a divalent organic group represented by the following chemical formula 4, which can provide a polymer for a liquid crystal aligning agent having various structures capable of exhibiting the above-described effects.
[ chemical formula 4]
Figure GDA0003922747360000051
In chemical formula 4, Q 1 To Q 4 At least one of which is nitrogen and the rest is carbon, Q 5 To Q 8 At least one of which is nitrogen and the others are carbon, and R 3 Is hydrogen or an alkyl group having 1 to 6 carbon atoms.
The functional group represented by chemical formula 4 has a structural feature in which two aromatic cyclic compounds, preferably heteroaromatic cyclic compounds, are bonded through a secondary amine group or a tertiary amine group. Thus, even when the same or higher level of alignment and afterimage characteristics are satisfied as a liquid crystal aligning agent, the voltage holding ratio can be improved to 94% or more, and thus excellent electrical characteristics can be achieved.
On the other hand, when two aromatic cyclic compounds are bonded by a single bond instead of a secondary amine group or a tertiary amine group, there may be a technical problem in that the alignment property of the liquid crystal alignment agent is poor and the voltage holding ratio is reduced to less than 80%.
In addition, when both of the two aromatic cyclic compounds bonded through the secondary amine group or the tertiary amine group do not contain a nitrogen atom, even if imidization reaction is performed on the polyamic acid or polyamic acid ester formed by the reaction between the amine and the acid anhydride, sufficient imidization reaction cannot be performed (for example, by heat treatment at 230 ℃). Therefore, there is a limit to decrease the imidization rate in the final liquid crystal alignment film. This seems to be due to differences in physical and chemical properties of amine, polyamic acid, and polyamic acid ester caused by structural differences of amine compounds.
Specifically, in chemical formula 4, Q 1 To Q 4 One of them may be nitrogen and the others may be carbon, Q 5 To Q 8 One of which may be nitrogen and the remainder may be carbon. More specifically, Q in chemical formula 4 1 To Q 4 In (1), Q 2 And Q 4 One of them may be nitrogen and the others may be carbon, Q 1 And Q 3 May be carbon. In addition, Q in chemical formula 4 5 To Q 8 In (1), Q 5 And Q 7 One of them may be nitrogen and the others may be carbon, Q 6 And Q 8 May be carbon.
Preferably, Q in chemical formula 4 1 To Q 4 In (1), Q 2 And Q 4 One of them may be nitrogen and the others may be carbon, Q 1 And Q 3 May be carbon. Meanwhile, in Q of chemical formula 4 5 To Q 8 In (1), Q 5 And Q 7 One of them may be nitrogen and the others may be carbon, Q 6 And Q 8 May beAnd (3) carbon.
That is, chemical formula 4 may have a structure in which a pyridine compound in which one of six carbons of benzene is substituted with nitrogen is asymmetrically bonded through a secondary amine or a tertiary amine. Accordingly, a liquid crystal display device using the polymer for a liquid crystal aligning agent of one embodiment can achieve high voltage holding ratio and liquid crystal alignment characteristics.
On the other hand, in chemical formula 4, when Q 1 And Q 3 One of them is nitrogen, or Q 6 And Q 8 When one of them is nitrogen, there may be a problem that the electrical characteristics and long-term reliability of the prepared alignment film gradually decrease.
In addition, in chemical formula 4, R 3 May be hydrogen.
Chemical formula 4 is a repeating unit derived from diamine that is a precursor for forming a polymer for a liquid crystal aligning agent, and is considered to be generated by using an asymmetric pyridine-based diamine as described below.
In view of the fact that the structure of the asymmetric pyridine diamine or the repeating unit derived therefrom and the effect resulting therefrom have not been recognized in the field of polymers for liquid crystal aligning agents previously known in the art, the repeating unit of chemical formula 4 and the diamine compound as a precursor thereof are considered to be novel.
In addition, chemical formula 4 may include a functional group represented by chemical formula 4-1 or chemical formula 4-2 below.
[ chemical formula 4-1]
Figure GDA0003922747360000061
[ chemical formula 4-2]
Figure GDA0003922747360000071
In chemical formulas 4-1 and 4-2, Q 1 To Q 8 And R is 3 The limitations of (2) include those described in chemical formula 4 above.
Accordingly, since chemical formula 4 includes a functional group represented by chemical formula 4-1 or chemical formula 4-2, a liquid crystal display device employing the polymer for a liquid crystal alignment agent of one embodiment can achieve high voltage holding ratio and liquid crystal alignment characteristics.
More specifically, chemical formula 4 may include a functional group represented by chemical formula 4-3 or chemical formula 4-4 below.
[ chemical formula 4-3]
Figure GDA0003922747360000072
[ chemical formula 4-4]
Figure GDA0003922747360000073
At the same time X 1 To X 3 Each independently may be a tetravalent organic group represented by the following chemical formula 5.
[ chemical formula 5]
Figure GDA0003922747360000081
/>
In chemical formula 5, R 9 To R 14 Each independently is hydrogen or an alkyl group having 1 to 10 carbon atoms, and L 2 Is any one selected from the following: direct bond, -O-, -CO-, -S-, -SO 2 -、-CR 15 R 16 -、-CONH-、-COO-、-(CH 2 ) b -、-O(CH 2 ) b O-、-COO-(CH 2 ) b -OCO-, phenylene or a combination thereof, wherein R 15 And R is 16 Each independently is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a fluoroalkyl group having 1 to 10 carbon atoms, and b is an integer of 1 to 10.
More preferably X 1 To X 3 Each independently is an organic group of the following chemical formula 5-1 derived from cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, the following chemical formula derived from 1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic dianhydrideAn organic group of formula 5-2, or derived from tetrahydro- [3,3' -bisfuran]-an organic group of the following chemical formula 5-3 of 2,2', 5' -tetraketone
[ chemical formula 5-1]
Figure GDA0003922747360000082
[ chemical formula 5-2]
Figure GDA0003922747360000083
[ chemical formulas 5-3]
Figure GDA0003922747360000091
Among the repeating units represented by chemical formula 1, chemical formula 2 and chemical formula 3, the polymer may contain 0 to 80mol%, or 0.1 to 65mol% of the repeating unit represented by chemical formula 1 as an imide repeating unit, based on the total repeating units.
As described above, when a polymer comprising a specific content of imide repeating units represented by chemical formula 1 is used, the polymer comprises a specific content of previously imidized imide repeating units. Therefore, although the high-temperature heat treatment step is omitted and light irradiation is immediately performed, a liquid crystal alignment film having excellent alignment characteristics and stability can be produced.
If the repeating unit represented by chemical formula 1 is contained in an amount below this range, sufficient alignment characteristics may not be obtained and alignment stability may deteriorate. If the repeating unit represented by chemical formula 1 is contained in an amount higher than this range, there is a problem in that the solubility may be lowered and thus it is difficult to prepare a stable alignment solution that can be coated. Therefore, in terms of providing a polymer for a liquid crystal aligning agent excellent in storage stability, electrical characteristics, alignment characteristics and alignment stability, it is preferable to include the repeating unit represented by chemical formula 1 in an amount within the above range.
Further, the repeating unit represented by chemical formula 2 or the repeating unit represented by chemical formula 3 may be contained in an appropriate amount according to desired characteristics.
Specifically, the repeating unit represented by chemical formula 2 may be included in an amount of 0 to 50mol%, preferably 0.1 to 30mol%, based on the total repeating units represented by chemical formulas 1 to 3. During the high-temperature heat treatment step after light irradiation, the conversion rate of the repeating unit represented by chemical formula 2 into imide is low, and therefore, if the content thereof exceeds the above range, the overall imidization rate is insufficient and the orientation stability may be lowered. Therefore, when the repeating unit represented by chemical formula 2 is used in the above range, it exhibits proper solubility, thereby providing a polymer for a liquid crystal aligning agent capable of achieving a high imidization rate while having excellent processing characteristics.
Further, the repeating unit represented by chemical formula 3 may be included in an amount of 10 to 100mol%, or 30 to 99.8mol%, based on the total repeating units represented by chemical formulas 1 to 3. When the repeating unit represented by chemical formula 3 is used in the above range, it exhibits excellent coating characteristics, thereby providing a polymer for a liquid crystal aligning agent capable of achieving a high imidization rate while having excellent processing characteristics.
The weight average molecular weight of the polymer used for the liquid crystal aligning agent may be 100g/mol to 200,000g/mol, or 100g/mol to 10,000g/mol. The weight average molecular weight means a weight average molecular weight in terms of polystyrene measured by GPC. In determining the weight average molecular weight in terms of polystyrene measured by the GPC method, a conventionally known analysis device, a detector such as a refractive index detector, and an analytical column can be used. Commonly applied temperature, solvent and flow conditions may be used. Specific examples of measurement conditions include a temperature of 30 ℃, chloroform solvent, and a flow rate of 1 mL/min.
Such a polymer can be used as a liquid crystal aligning agent to provide a liquid crystal alignment film achieving excellent stability and reliability.
Examples of the method for preparing the polymer for the liquid crystal aligning agent are not particularly limited, and for example, a method including the steps of: reacting a heteroaromatic compound of formula 6 below with a heteroaromatic compound of formula 7 to produce a compound of formula 8 below; reducing the compound of chemical formula 8 to prepare a diamine of the following chemical formula 9; and reacting the diamine of chemical formula 9 with a tetracarboxylic acid or an anhydride thereof to prepare a polymer for a liquid crystal aligning agent.
[ chemical formula 6]
Figure GDA0003922747360000101
In chemical formula 6, R 21 Is a halogen atom, R 22 Is a functional group of nitrogen oxide
Z 1 To Z 4 At least one of which is nitrogen and the remainder are carbon.
[ chemical formula 7]
Figure GDA0003922747360000102
In chemical formula 7, R 3 Is hydrogen or alkyl having 1 to 10 carbon atoms, R 23 Is an amino or nitroxide functional group and Z 5 To Z 8 At least one of which is nitrogen and the remainder are carbon.
[ chemical formula 8]
Figure GDA0003922747360000103
[ chemical formula 9]
Figure GDA0003922747360000111
Preferably, in chemical formula 6, R 21 Is a chlorine atom, R 22 Is nitro, Z 1 And Z 3 One of them is nitrogen and the others are carbon, and Z 2 And Z 4 May beAnd (3) carbon. That is, preferable examples of chemical formula 6 include 2-chloro-5-nitropyridine, 2-chloro-4-nitropyridine, and the like.
Meanwhile, in chemical formula 7, Z 5 And Z 7 One of them is nitrogen and the others are carbon, Z 6 And Z 8 Is carbon, R 3 Is hydrogen and R 23 May be a nitro group. That is, preferable examples of chemical formula 7 include 5-nitropyridin-2-amine and the like.
Specifically, in the step of preparing the compound of chemical formula 8, the compound of chemical formula 8 may be prepared by reacting the heteroaromatic compound of chemical formula 6 with the heteroaromatic compound of chemical formula 7. Specifically, it is possible to perform a process in which the halogen element R contained in the heteroaromatic compound of chemical formula 6 21 Substituted reaction with nitrogen contained in the heteroaromatic compound of chemical formula 7.
The reaction may be carried out in the presence of a tertiary amine catalyst at 50 to 150 ℃ for 10 to 20 hours. The reaction may be carried out in the presence of various organic solvents previously known in the art, and specific examples of the organic solvents include ethyl acetate, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ -butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisopentyl ketone, methylisopropylketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents may be used alone or in combination.
In the nitroxide functional group, nitroxide is a compound in which a nitrogen atom and an oxygen atom are bonded, and the nitroxide functional group means a functional group including nitroxide in the functional group. As examples of nitroxide functionalities, nitro (-NO) groups can be used 2 ) Etc.
Can be prepared byThe compound of chemical formula 8 undergoes a reduction reaction to prepare a diamine compound of chemical formula 9. Specifically, when the nitroxide functional group R is contained in the compound of formula 8 22 Or R is 23 When reduced to a primary amino group under reducing conditions, diamine compounds can be synthesized.
The reduction reaction may be carried out under mild conditions of 10 to 15 hours at room temperature in the presence of a palladium/carbon catalyst. The reaction may be carried out in the presence of various organic solvents previously known in the art, and specific examples of the organic solvents include ethyl acetate, tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ -butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisopentyl ketone, methylisopropylketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents may be used alone or in combination.
Z described in chemical formulas 8 and 9 1 To Z 8 、R 3 、R 22 And R is 23 Including those described above in formulas 6 and 7.
Specific examples of the compound of chemical formula 9 include compounds represented by the following chemical formulas 9-1 or 9-2.
[ chemical formula 9-1]
Figure GDA0003922747360000121
[ chemical formula 9-2]
Figure GDA0003922747360000122
The diamine of chemical formula 9 prepared by the above step may be reacted with a tetracarboxylic acid or an anhydride thereof, such as pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, or cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, or 1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic dianhydride, tetrahydro- [3,3' -bisfuran ] -2,2', 5' -tetraketone, or the like, which is generally used for preparing polyamic acid, to prepare a polymer comprising amic acid, amic acid ester, or a mixture thereof.
Alternatively, if necessary, various types of diamine compounds generally known in the art related to liquid crystal aligning agents (e.g., p-phenylenediamine, 4-oxydiphenylamine, 4' -methylenediphenylamine, etc.) may be mixed to prepare amic acids, amic acid esters, or mixtures thereof, in addition to the diamine of chemical formula 9 prepared through the above steps.
The reaction conditions may be appropriately adjusted with reference to the production conditions of polyamic acid known in the art.
Meanwhile, according to another embodiment of the present invention, there is provided a liquid crystal aligning agent composition comprising the above polymer.
Such a liquid crystal aligning agent composition may be provided by various methods known in the art, except that it contains the above-mentioned polymer.
As a non-limiting example, the above-described polymers may be dissolved or dispersed in an organic solvent to provide a liquid crystal aligning agent composition.
Specific examples of the organic solvent include N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisopentyl ketone, methylisopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents may be used alone or in combination.
In addition, the liquid crystal aligning agent composition may contain other components in addition to the polymer and the organic solvent. In one non-limiting example, when coating the liquid crystal aligning agent composition, such additives may also be included: which can improve film thickness uniformity and surface smoothness, improve adhesion between a liquid crystal alignment film and a substrate, or change dielectric constant and conductivity of the liquid crystal alignment film, or increase compactness of the liquid crystal alignment film. Examples of such additives include various solvents, surfactants, silane-based compounds, dielectrics, crosslinking compounds, and the like.
Method for preparing liquid crystal alignment film
Further, the present invention provides a method for preparing a liquid crystal alignment film, comprising the steps of: coating a liquid crystal aligning agent composition onto a substrate to form a coating film (step 1); drying the coated film (step 2); immediately after the drying step, irradiating the coating film with light or rubbing the coating film to perform an orientation treatment (step 3); and heat-treating and curing the oriented coating film (step 4).
Step 1 is a step of coating the above liquid crystal aligning agent composition onto a substrate to form a coating film.
The method of applying the liquid crystal aligning agent composition to the substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexography, inkjet printing, or the like may be used.
In addition, the liquid crystal aligning agent composition may be a liquid crystal aligning agent composition dissolved or dispersed in an organic solvent. Specific examples of the organic solvent include: n, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1, 3-dimethyl-imidazolidinone, ethylpentyl ketone, methylnonyl ketone, methylethyl ketone, methylisopentyl ketone, methylisopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, and the like. These solvents may be used alone or in combination.
In addition, the liquid crystal aligning agent composition may contain other components in addition to the organic solvent. In one non-limiting example, when coating the liquid crystal aligning agent composition, such additives may also be included: which can improve film thickness uniformity and surface smoothness, or improve adhesion between a liquid crystal alignment film and a substrate, or change dielectric constant and conductivity of the liquid crystal alignment film, or increase compactness of the liquid crystal alignment film. Examples of such additives include various solvents, surfactants, silane-based compounds, dielectrics, crosslinking compounds, and the like.
Step 2 is a step of drying a coating film formed by coating a liquid crystal aligning agent composition onto a substrate.
The step of drying the coating film may be performed by using a method such as heating the coating film or vacuum evaporation, and is preferably performed at 50 to 150 ℃, or 60 to 140 ℃.
Step 3 is a step of irradiating the coating film with light or rubbing the coating film to perform an orientation treatment immediately after the drying step.
In this specification, "irradiating the coating film immediately after the drying step" means irradiating the film immediately after the drying with light without performing heat treatment at a temperature higher than that of the drying step, and steps other than the heat treatment may be added.
More specifically, when a liquid crystal alignment film is prepared by using a conventional liquid crystal alignment agent comprising a polyamic acid or a polyamic acid ester, it includes a step of irradiating light after substantially performing a high-temperature heat treatment to imidize the polyamic acid. However, when the liquid crystal alignment film is prepared using the liquid crystal alignment agent of the above-described one embodiment, it does not include a heat treatment step, and light is directly irradiated to perform alignment treatment, and then the alignment-treated coating film is cured by the heat treatment, so that the liquid crystal alignment film can be prepared.
In addition, in the alignment treatment step, the light irradiation may be performed by irradiating polarized ultraviolet rays having a wavelength of 150nm to 450 nm. In this case, the exposure intensity may vary depending on the kind of polymer used for the liquid crystal aligning agent, and preferably, 10mJ/cm may be irradiated 2 To 10J/cm 2 Or 30mJ/cm 2 To 2J/cm 2 Is a function of the energy of the (c).
Regarding ultraviolet rays, polarized ultraviolet rays selected from ultraviolet rays subjected to polarization treatment by passing through or reflecting by the following polarization means are irradiated to perform the orientation treatment: a polarizing device using a substrate in which a dielectric anisotropic material is coated onto a surface of a transparent substrate (e.g., quartz glass, soda lime-free glass, etc.); a polarizing plate on which aluminum or metal wires are finely deposited; or a Brewster polarizing device using reflection of quartz glass, etc. Here, the polarized ultraviolet rays may be irradiated perpendicularly to the substrate surface, or may be irradiated by directing the incident angle toward a specific angle. By this method, the coating film is imparted with the orientation ability of the liquid crystal molecules.
Further, in the orientation treatment step, a method using a rubbing cloth may be employed for the rubbing treatment. More specifically, in the rubbing treatment, the surface of the coating film after the drying step may be rubbed in one direction while rotating a rubbing roller in which a rubbing cloth is attached to a metal roller.
Step 4 is a step of heat-treating and curing the orientation-treated coating film.
The step of heat-treating and curing the alignment-treated coating film is a step performed after light irradiation even in a conventional method for preparing a liquid crystal alignment film using a polymer for a liquid crystal alignment agent containing polyamic acid or polyamic acid ester, and is different from a heat-treating step performed by coating a liquid crystal alignment agent composition onto a substrate and then imidizing the liquid crystal alignment agent before or simultaneously with the irradiation of light.
In this case, the heat treatment may be performed by a heating device such as a hot plate, a hot air circulation furnace, an infrared furnace, or the like, and the heat treatment is preferably performed at a temperature of 150 to 300 ℃, or 180 to 250 ℃.
Meanwhile, if necessary, after the step of drying the coating film (step 2), the method may further include heat-treating the coating film at a temperature equal to or higher than that of the drying step immediately after the drying step. The heat treatment may be performed by heating means such as a hot plate, a hot air circulation furnace, and an infrared furnace, and is preferably performed at a temperature of 150 to 250 ℃. In this process, the liquid crystal aligning agent may be imidized.
That is, the method for preparing a liquid crystal alignment film may include the steps of: coating the above liquid crystal aligning agent composition onto a substrate to form a coating film (step 1); drying the coated film (step 2); immediately after the drying step, heat-treating the coating film at a temperature equal to or higher than the temperature of the drying step (step 3); irradiating the heat-treated coating film or the friction coating film with light to perform an orientation treatment (step 4); and heat-treating and curing the oriented coating film (step 5).
Liquid crystal alignment film
Further, the present invention can provide a liquid crystal alignment film produced according to the above-described method for producing a liquid crystal alignment film.
As described above, when a liquid crystal aligning agent composition including a polymer for a liquid crystal aligning agent containing at least one repeating unit selected from the group consisting of a repeating unit represented by chemical formula 1, a repeating unit represented by chemical formula 2, and a repeating unit represented by chemical formula 3 is used, a liquid crystal aligning film having excellent alignment characteristics and electrical characteristics can be prepared.
Liquid crystal display device having a light shielding layer
Further, the present invention provides a liquid crystal display device including the above liquid crystal alignment film.
The liquid crystal alignment film may be introduced into the liquid crystal cell by a known method, and the liquid crystal cell may also be introduced into the liquid crystal display device by a known method. The liquid crystal alignment film may be prepared from the liquid crystal alignment agent composition of another embodiment, thereby achieving excellent stability as well as excellent physical properties. Specifically, a liquid crystal display device may be provided: it can have a high voltage holding ratio at high temperature and low frequency, have excellent electrical characteristics, reduce image sticking (afterimage) phenomenon or performance degradation of contrast, and have excellent film strength.
Advantageous effects
According to the present invention, it is possible to provide a polymer for a liquid crystal aligning agent having excellent liquid crystal characteristics, durability and electric characteristics, a method for preparing the liquid crystal aligning agent composition, and a method for preparing the same.
Detailed Description
The present invention will be described in more detail by way of examples. However, these examples are given for illustrative purposes only and the scope of the present invention is not intended to be limited by these examples.
< preparation example: preparation of diamine-
Preparation example 1
Figure GDA0003922747360000171
15.0g (95 mmol) of 2-chloro-5-nitropyridine (compound 1) and 13.8g (99 mmol) of 5-nitropyridin-2-amine (compound 2) are completely dissolved in 200mL of Dimethylformamide (DMF). 23.4g (200 mmol) of Triethylamine (TEA) was then added thereto and stirred at 90℃for 16 hours. When the reaction was complete, the reaction product was poured into a container containing 500mL of water and stirred for 1 hour. The solid obtained by filtration was washed with 200mL of ultrapure water to synthesize 15g (42.5 mmol) of compound 3 (yield: 45%).
Figure GDA0003922747360000172
Compound 3 was dissolved in 200mL of Tetrahydrofuran (THF). To this was added 0.8g of palladium (Pd)/carbon (C) and stirred under a hydrogen atmosphere for 12 hours. After the completion of the reaction, the reaction mixture was filtered through a celite pad, and the filtrate was concentrated to prepare 9.0g of the diamine of preparation 1 (compound 4) (yield: 60%).
Preparation example 2
Figure GDA0003922747360000173
A diamine of production example 2 (Compound 7) was produced in the same manner as in production example 1, except that 2-chloro-4-nitropyridine (Compound 5) was used instead of 2-chloro-5-nitropyridine (Compound 1).
Synthesis examples and comparative synthesis examples: synthesis of Polymer for liquid Crystal alignment agent
Synthesis example 1: polymer P-1 for liquid Crystal alignment
1.408g (7 mmol) of the diamine prepared in preparation example 1 was completely dissolved in 15.37g of anhydrous N-methylpyrrolidone (NMP).
Then, 1.304g (6.65 mmol) of cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA) was added to the solution under ice bath and stirred at room temperature for 16 hours to prepare polymer P-1 for liquid crystal alignment.
Synthesis example 2: polymer P-2 for liquid Crystal alignment
Polymer P-2 for liquid crystal alignment was prepared in the same manner as in Synthesis example 1, except that the diamine prepared in preparation example 2 was used instead of the diamine prepared in preparation example 1.
Synthesis example 3: polymer P-3 for liquid Crystal alignment
Polymer P-3 for liquid crystal alignment was prepared in the same manner as in Synthesis example 1, except that 1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DMCBDA) was used instead of cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA).
Synthesis example 4: polymer P-4 for liquid Crystal alignment
Polymer P-4 for liquid crystal alignment was prepared in the same manner as in Synthesis example 2, except that 1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (DMCBDA) was used instead of cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA).
Synthesis example 5: polymer P-5 for liquid Crystal alignment
Polymer P-5 for liquid crystal alignment was prepared in the same manner as in Synthesis example 1, except that tetrahydro- [3,3' -bisfuran ] -2,2', 5' -tetraketone (BT 100) was used instead of cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA).
Synthesis example 6: polymer P-6 for liquid Crystal alignment
Polymer P-6 for liquid crystal alignment was prepared in the same manner as in Synthesis example 2, except that tetrahydro- [3,3' -bisfuran ] -2,2', 5' -tetraketone (BT 100) was used instead of cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride (CBDA).
Comparative synthesis example 1: polymer R-1 for liquid crystal alignment
Polymer R-1 for liquid crystal alignment was prepared in the same manner as in Synthesis example 1 except that 6- (4-aminophenyl) pyridin-3-amine represented by the following chemical formula A was used instead of the diamine prepared in preparation example 1.
[ chemical formula A ]
Figure GDA0003922747360000191
Comparative synthesis example 2: polymer R-2 for liquid crystal alignment
Polymer R-2 for liquid crystal alignment was prepared in the same manner as in Synthesis example 1, except that 4,4' -diaminodiphenylamine represented by the following chemical formula B was used instead of the diamine prepared in preparation example 1.
[ chemical formula B ]
Figure GDA0003922747360000192
< examples and comparative examples: preparation of liquid Crystal alignment agent-
Example 1
20g of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1 was dissolved in a mixed solvent of 8.65g of NMP, 19.95g of GBL and 11.4g of 2-butoxyethanol to obtain a 5 wt% solution. Then, the obtained solution was subjected to pressure filtration through a filter made of poly (tetrafluoroethylene) having a pore size of 0.1 μm to prepare a liquid crystal aligning agent A-1.
Example 2
A liquid crystal aligning agent A-2 was prepared in the same manner as in example 1, except that the polymer P-2 for a liquid crystal aligning agent of Synthesis example 2 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Example 3
A liquid crystal aligning agent A-3 was prepared in the same manner as in example 1, except that the polymer P-3 for a liquid crystal aligning agent of Synthesis example 3 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Example 4
A liquid crystal aligning agent A-4 was prepared in the same manner as in example 1, except that the polymer P-4 for a liquid crystal aligning agent of Synthesis example 4 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Example 5
A liquid crystal aligning agent A-5 was prepared in the same manner as in example 1, except that the polymer P-5 for a liquid crystal aligning agent of Synthesis example 5 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Example 6
A liquid crystal aligning agent A-6 was prepared in the same manner as in example 1 except that the polymer P-6 for a liquid crystal aligning agent of Synthesis example 6 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Comparative example 1
A liquid crystal aligning agent B-1 was prepared in the same manner as in example 1, except that the polymer R-1 for a liquid crystal aligning agent of comparative Synthesis example 1 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
Comparative example 2
A liquid crystal aligning agent B-2 was prepared in the same manner as in example 1, except that the polymer R-2 for a liquid crystal aligning agent of comparative Synthesis example 2 was used instead of the polymer P-1 for a liquid crystal aligning agent of Synthesis example 1.
< experimental example: measurement of physical Properties of liquid Crystal alignment Agents obtained in examples and comparative examples-
Liquid crystal cells were prepared by using the liquid crystal aligning agents obtained in examples and comparative examples. The physical properties of each liquid crystal alignment unit were measured by the following methods, and the results are shown in table 1 below.
Specifically, the liquid crystal aligning agent compositions prepared in examples and comparative examples were coated onto each of an upper substrate and a lower substrate for a Voltage Holding Ratio (VHR) using a spin coating method, in which an ITO electrode having a thickness of 60nm and an area of 1cm×1cm was patterned on a rectangular glass substrate having a size of 2.5cm×2.7 cm. Then, the substrate having the liquid crystal aligning agent composition coated thereon was placed on a hot plate of about 80 ℃ and dried for 2 minutes to evaporate the solvent. In order to subject the thus obtained coating film to an orientation treatment, an exposure apparatus having a linear polarizer adhered thereto was used at 0.25J/cm 2 Is irradiated with 254nm ultraviolet rays to the coating film of each of the upper plate/lower plate. Subsequently, the upper/lower plates subjected to the orientation treatment were calcined (cured) in an oven at about 230 ℃ for 15 minutes to obtain a coating film having a thickness of 0.1 μm. Then, a sealant impregnated with a spherical spacer having a size of 4.5 μm was applied to the edge of the upper plate except the liquid crystal injection hole. Then, alignment films formed on the upper and lower plates are aligned so that they face each other and alignment directions are aligned with each other, and then the upper and lower plates are alignedBond together and cure the sealant to make an empty space. Then, liquid crystal is injected into the empty cell to prepare a liquid crystal alignment cell.
1. Evaluation of liquid Crystal alignment Properties
Polarizers were adhered to the upper and lower plates of the above-prepared liquid crystal cell so as to be perpendicular to each other. Then the liquid crystal cell with the attached polarizing plate was placed at a luminance of 7000cd/m 2 And the light leakage is observed with naked eyes. At this time, if the alignment characteristics of the liquid crystal alignment film are excellent and the liquid crystal alignment is good, light does not pass through the upper and lower polarizing plates that are perpendicularly adhered to each other, and darkness without defects is observed. In this case, the alignment characteristic is evaluated as "good", and when light leakage such as a liquid crystal flow mark or a bright point is observed, it is evaluated as "poor". The results are shown in table 1 below.
2. Voltage Holding Ratio (VHR)
For the liquid crystal alignment unit, the voltage holding ratio was measured at 1Hz and 60 ℃ using a 6254C device available from TOYO Corporation as a measuring instrument.
Ac afterimage
The polarizing plates are adhered to the upper and lower plates of the liquid crystal cell so as to be perpendicular to each other. Adhering the liquid crystal cell with the polarizing plate adhered thereto to 7000cd/m 2 And measures the brightness in the black mode using the apparatus PR-880 for measuring brightness. Then, the liquid crystal cell was driven at room temperature for 24 hours with an AC voltage of 5V. Thereafter, the luminance in the black mode was measured in the same manner as described above in a state where the voltage of the liquid crystal cell was turned off. The difference between the initial luminance (L0) measured before driving the liquid crystal cell and the final luminance (L1) measured after driving the liquid crystal cell is divided by the value of the initial luminance (L0) and multiplied by 100, thereby calculating the luminance fluctuation ratio. When the calculated luminance fluctuation ratio is closer to 0%, it means that the orientation stability is excellent. The afterimage level is evaluated by the measurement result of such a luminance fluctuation ratio according to the following criteria.
Excellent: the brightness fluctuation rate is less than 10%
Common: the brightness fluctuation rate is 10 to 20 percent
4. Imidization conversion (%)
The FT-IR spectra of the liquid crystal alignment films obtained from the liquid crystal alignment agent compositions of examples and comparative examples were measured by the ATR method, and the ratio of imide structures in polymer molecules contained in the alignment films was measured.
TABLE 1
Measurement results of experimental examples of examples and comparative examples
Figure GDA0003922747360000221
* Chemical formula a:6- (4-aminophenyl) pyridin-3-amine
* Chemical formula B:4,4' -diaminodiphenylamine
* CBDA: cyclobutane-1, 2,3, 4-tetracarboxylic dianhydride
* DMCBDA:1, 3-dimethylcyclobutane-1, 2,3, 4-tetracarboxylic dianhydride
* BT100: tetrahydro- [3,3' -bisfuran ] -2,2', 5' -tetraketone
As shown in table 1, it was determined that the liquid crystal alignment unit obtained by using the polymer synthesized from the diamine having a specific structure obtained in preparation examples 1 and 2 exhibited excellent alignment characteristics and afterimage characteristics, and the Voltage Holding Ratio (VHR) was as high as 94% or more, thereby achieving enhanced electrical characteristics.
In contrast, it was determined that the liquid crystal aligning agent of comparative example 1 did not contain diamine having the same structure as that of preparation examples 1 and 2 in the reactant during preparation of the polymer, and exhibited a Voltage Holding Ratio (VHR) of 78%, which was significantly lower than that of the examples.
Comparative example 2 was determined to exhibit excellent alignment characteristics, afterimage characteristics, and VHR characteristics, but did not contain diamine having the structures shown in preparation examples 1 and 2, and thus exhibited a relatively low imidization ratio of 90% at 230 ℃ as compared with the examples.

Claims (12)

1. A liquid crystal aligning agent composition comprising a polymer comprising at least one selected from the group consisting of: a repeating unit represented by the following chemical formula 1, a repeating unit represented by the following chemical formula 2, and a repeating unit represented by the following chemical formula 3,
[ chemical formula 1]
Figure FDA0004103503390000011
[ chemical formula 2]
Figure FDA0004103503390000012
[ chemical formula 3]
Figure FDA0004103503390000013
Wherein, in chemical formulas 1 to 3,
R 1 and R is 2 At least one of which is an alkyl group having 1 to 10 carbon atoms and the remainder being hydrogen,
X 1 to X 3 Each independently is a tetravalent organic group represented by the following chemical formula 5-3,
[ chemical formulas 5-3]
Figure FDA0004103503390000021
and
Y 1 To Y 3 Each independently is a divalent organic group represented by the following chemical formula 4-2,
[ chemical formula 4-2]
Figure FDA0004103503390000022
Wherein, in chemical formula 4-2,
Q 1 to Q 4 At least one of which is nitrogen and the remainder carbon,
Q 5 to Q 8 At least one of which is nitrogen and the rest is carbon, and
R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms.
2. The liquid crystal aligning agent composition according to claim 1, wherein Q in chemical formula 4-2 1 To Q 4 In (1), Q 2 And Q 4 One of them is nitrogen and the others are carbon, and Q 1 And Q 3 Is carbon.
3. The liquid crystal aligning agent composition according to claim 1, wherein Q in chemical formula 4-2 5 To Q 8 In (1), Q 5 And Q 7 One of them is nitrogen and the others are carbon, and Q 6 And Q 8 Is carbon.
4. The liquid crystal aligning agent composition according to claim 1, wherein in chemical formula 4-2, R 3 Is hydrogen.
5. The liquid crystal aligning agent composition according to claim 1, wherein the weight average molecular weight of the polymer for a liquid crystal aligning agent is 100g/mol to 200,000g/mol.
6. A method for preparing a liquid crystal alignment film, comprising the steps of:
applying the liquid crystal aligning agent composition according to any one of claims 1 to 5 onto a substrate to form a coating film;
drying the coated film;
irradiating the coating film with light or rubbing the coating film to perform an orientation treatment immediately after the drying step; and
the orientation-treated coating film is subjected to heat treatment and curing.
7. The method for producing a liquid crystal alignment film according to claim 6, wherein the liquid crystal alignment agent composition is dissolved or dispersed in an organic solvent.
8. The method for producing a liquid crystal alignment film according to claim 6, wherein the step of drying the coating film is performed at 50 ℃ to 150 ℃.
9. The method for producing a liquid crystal alignment film according to claim 6, wherein in the alignment treatment step, light irradiation is performed by irradiating polarized ultraviolet rays having a wavelength of 150nm to 450 nm.
10. The method for producing a liquid crystal alignment film according to claim 6, wherein in the step of heat-treating and curing the coating film, the heat-treating temperature is 150 ℃ to 300 ℃.
11. A liquid crystal alignment film produced by the method for producing a liquid crystal alignment film according to claim 6.
12. A liquid crystal display device comprising the liquid crystal alignment film according to claim 11.
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